JPH07104321A - Electrochromic display element - Google Patents
Electrochromic display elementInfo
- Publication number
- JPH07104321A JPH07104321A JP5271251A JP27125193A JPH07104321A JP H07104321 A JPH07104321 A JP H07104321A JP 5271251 A JP5271251 A JP 5271251A JP 27125193 A JP27125193 A JP 27125193A JP H07104321 A JPH07104321 A JP H07104321A
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte
- driving
- sodium
- cyclic
- current value
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 tetrafluoroborate Chemical compound 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 9
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- OJTMBXWTXBFVQN-UHFFFAOYSA-N iron;1,10-phenanthroline Chemical compound [Fe].C1=CN=C2C3=NC=CC=C3C=CC2=C1 OJTMBXWTXBFVQN-UHFFFAOYSA-N 0.000 claims description 3
- 238000006479 redox reaction Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 16
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 239000011780 sodium chloride Substances 0.000 abstract description 8
- 150000001450 anions Chemical class 0.000 abstract description 6
- 239000003115 supporting electrolyte Substances 0.000 abstract description 6
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 abstract description 5
- 150000001768 cations Chemical class 0.000 abstract description 4
- 238000002484 cyclic voltammetry Methods 0.000 abstract description 4
- 239000011734 sodium Substances 0.000 abstract description 4
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 abstract description 4
- 229910001488 sodium perchlorate Inorganic materials 0.000 abstract description 4
- 230000007423 decrease Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 2
- 238000001075 voltammogram Methods 0.000 abstract description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract 1
- 238000005259 measurement Methods 0.000 abstract 1
- 229910001415 sodium ion Inorganic materials 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 229910020808 NaBF Inorganic materials 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000003566 sealing material Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 3
- 229960003351 prussian blue Drugs 0.000 description 3
- 239000013225 prussian blue Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電解析出法により成膜
が可能な鉄−フェナントロリン錯体を用い、その酸化還
元反応を利用した、赤と無色の表示が可能なエレクトロ
クロミック表示素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochromic display device which uses an iron-phenanthroline complex which can be formed into a film by an electrolytic deposition method and uses its redox reaction to display red and colorless.
【０００２】[0002]
【従来の技術】従来、赤色エレクトロクロミック材料で
あるフェノール基を有するバソフェナントロリン鉄錯体
は、図１に示す結合構造のトリス（バソフェナントロリ
ンジフェノール）鉄（II）錯体（以下Ｆｅ（ＢＰＤＰ）
3 と示す）であって、本出願人が先に提案した特開平４
−２９２２０号に示されるように電解析出法により成膜
され、支持電解質として過塩素酸ナトリウム（ＮａＣｌ
Ｏ4 ）を０．１ｍｏｌ／ｌの濃度で含むアセトニトリル
電解液中において、プルシアンブルーを対向極として一
万回以上の色変化（赤と薄黄色）と０．５秒以下の応答
速度を達成することができた。2. Description of the Related Art Conventionally, a bathophenanthroline iron complex having a phenol group, which is a red electrochromic material, is a tris (vasophenanthroline diphenol) iron (II) complex (hereinafter referred to as Fe (BPDP)) having a bond structure shown in FIG.
3 )), which was previously proposed by the present applicant.
No. 29220, a film is formed by an electrolytic deposition method, and sodium perchlorate (NaCl) is used as a supporting electrolyte.
In an acetonitrile electrolyte containing O 4 ) at a concentration of 0.1 mol / l, a color change (red and light yellow) of 10,000 times or more and a response speed of 0.5 seconds or less are achieved with Prussian blue as the counter electrode. I was able to.
【０００３】しかしこのＦｅ（ＢＰＤＰ）3 の膜は、図
２に示す様な片側に透明導電膜１、７を形成した透明基
板１、８のそれぞれの内側に表示極エレクトロクロミッ
ク材料４、対向極エレクトロクロミック材料６を設け
て、背景材５を介して対向させ、上下をシール材３で囲
んだ空間に電解液９を充填したエレクトロクロミック表
示素子において、駆動用電解液溶媒９にアセトニトリル
（接着剤の剥離液に使用される）を使用すると、それに
耐えられるシール材３が無いため、素子の構成が困難で
あるという問題があった。However, this Fe (BPDP) 3 film has a display electrode electrochromic material 4 and a counter electrode on the inside of each of transparent substrates 1 and 8 having transparent conductive films 1 and 7 formed on one side as shown in FIG. In an electrochromic display element in which an electrochromic material 6 is provided, and the electrodes are opposed to each other with a background material 5 in between, and a space surrounded by a sealing material 3 is filled with an electrolyte solution 9, an acetonitrile (adhesive Used in the stripping solution), there is a problem that the construction of the element is difficult because there is no sealing material 3 that can withstand it.
【０００４】この駆動用電解液の問題は、エレクトロク
ロミック表示素子を構成する上で非常に重要なポイント
である。一方電解液９に水溶液が使用できれば、様々な
接着剤（例えばＵＶ硬化型）をシール材３として使用で
きるため、大きなメリットとなる。ところが以前の実験
では、表示極材料４であるＦｅ（ＢＰＤＰ）3 は、対向
極材料６にプルシアンブルーを使用して塩化ナトリウム
（ＮａＣｌ）を０．１ｍｏｌ／ｌの濃度に含む水溶液中
で駆動すると著しい特性劣化を起すことが確認されたた
め、駆動用電解液として水が使用できなかった。The problem of the driving electrolyte is a very important point in constructing an electrochromic display device. On the other hand, if an aqueous solution can be used as the electrolytic solution 9, various adhesives (for example, UV curing type) can be used as the sealing material 3, which is a great advantage. However, in the previous experiment, when the display electrode material Fe (BPDP) 3 was driven in an aqueous solution containing sodium chloride (NaCl) at a concentration of 0.1 mol / l using Prussian blue as the counter electrode material 6. Since it was confirmed that the characteristics were remarkably deteriorated, water could not be used as the driving electrolytic solution.
【０００５】ところで、Ｆｅ（ＢＰＤＰ）3 膜は、鉄錯
体が２価から３価へ酸化されることにより赤色から薄黄
色に変化し、再還元されることにより元の赤色に戻る。
この一連の反応を化１に示す。By the way, the Fe (BPDP) 3 film changes from red to light yellow when the iron complex is oxidized from divalent to trivalent, and returns to the original red by being reduced again.
This series of reactions is shown in Chemical formula 1.
【０００６】[0006]
【化１】 [Chemical 1]
【０００７】上記化１式からわかるように、消色時のＦ
ｅ（ＢＰＤＰ）3 膜は＋に帯電しているため、その電荷
を補償するための−電荷すなわちアニオンを膜中に取り
込まなければならない。また着色時にはアニオンを電解
液へ放出しなければ元の赤色に戻れない。従って繰り返
し駆動の安定性は、アニオンの種類にかなりの影響を受
けるものと考えられる。As can be seen from the above formula 1, F at the time of erasing
Since the e (BPDP) 3 film is positively charged, a − charge, that is, an anion, must be incorporated into the film to compensate the charge. Also, at the time of coloring, the original red color cannot be restored unless the anions are released into the electrolytic solution. Therefore, the stability of repeated driving is considered to be significantly affected by the type of anion.
【０００８】[0008]
【発明が解決しようとする課題】解決しようとする課題
は、Ｆｅ（ＢＰＤＰ）3 を表示極材料として構成された
エレクトロクロミック表示素子の繰り返し駆動の安定性
向上のために、最適な支持電解質を見つけ出すことであ
る。The problem to be solved is to find an optimum supporting electrolyte in order to improve the stability of repeated driving of an electrochromic display device composed of Fe (BPDP) 3 as a display electrode material. That is.
【０００９】[0009]
【問題を解決するための手段】本発明は、Ｆｅ（ＢＰＤ
Ｐ）3 に組み合わされる支持電解質を従来のＮａＣｌか
ら四フッ化ホウ素酸塩（ＮａＢＦ4 ）に変更すること
で、繰り返し駆動寿命の問題を改善するものである。The present invention relates to Fe (BPD
By changing the supporting electrolyte combined with P) 3 from conventional NaCl to tetrafluoroborate (NaBF 4 ), the problem of repeated driving life is improved.
【００１０】[0010]
【実施例】以下に実施した実験例を実施例として述べ
る。検討した駆動用支持電解質は、カチオン（陽イオ
ン）をナトリウム（Ｎａ+ ）、濃度を０．１ｍｏｌ／ｌ
に固定し、アニオンの異なる支持電解質を用意した。こ
の電解質は、塩化ナトリウム（ＮａＣｌ）、過塩素酸ナ
トリウム（ＮａＣｌＯ4 ）、硝酸ナトリウム（ＮａＮＯ
3 ）、四フッ化ホウ素酸ナトリウム（ＮａＢＦ4 ）の４
種類である。評価方法はＦｅ（ＢＰＤＰ）3 膜を成膜し
た電極についてサイクリックボルタンメトリーを連続し
て測定し、得られたボルタモグラムのピーク電流値の変
化を追跡することによって繰り返し駆動の安定性を評価
した。サイクリックボルタンメトリーは３電極法にて実
施し、対極には白金そして参照電極には飽和カロメル電
極を使用した。また、この時の走査速度は２０ｍＶ／ｓ
ｅｃ、走査電位幅は０Ｖ←→＋１．５Ｖｖｓにて実施し
た。EXAMPLES Examples of experiments conducted below will be described as examples. The supporting electrolyte for driving examined was sodium (Na + ) as a cation (cation) and a concentration of 0.1 mol / l.
And supporting electrolytes having different anions were prepared. This electrolyte is sodium chloride (NaCl), sodium perchlorate (NaClO 4 ), sodium nitrate (NaNO
3 ), 4 of sodium tetrafluoroborate (NaBF 4 )
It is a kind. As the evaluation method, cyclic voltammetry was continuously measured for the electrode on which the Fe (BPDP) 3 film was formed, and the stability of repeated driving was evaluated by tracking the change in the peak current value of the obtained voltammogram. Cyclic voltammetry was performed by the three-electrode method, using platinum as the counter electrode and a saturated calomel electrode as the reference electrode. The scanning speed at this time is 20 mV / s.
ec, the scanning potential width was 0V ← → + 1.5Vvs.
【００１１】その結果、図３に示されるように、ほとん
どの場合においてサイクリックボルタモグラムの電流値
が減少するなかでＮａＢＦ4 のみ低下率が少なく、繰り
返し寿命回数が数倍改善される結果が得られた。この時
Ｆｅ（ＢＰＤＰ）3 の繰り返し駆動に必要なイオンは陰
イオンであるため、ＢＦ4 塩であれば対陽イオンはナト
リウムに限定されるものではなく、Ｈ+ 、Ｌｉ+ 、
Ｋ+ 、Ｒｂ+ などであっても問題ない。またＮａＢＦ4
の添加濃度は０．０１ｍｏｌ／ｌ〜１ｍｏｌ／ｌの範囲
内であれば問題なく駆動可能であるが、特に０．０５ｍ
ｏｌ／ｌ〜０．５ｍｏｌ／ｌの範囲であることが望まし
い。As a result, as shown in FIG. 3, in most cases, while the current value of the cyclic voltammogram decreased, only NaBF 4 showed a small decrease rate and the number of times of repeated life was improved several times. It was At this time, since the ion required for repeatedly driving Fe (BPDP) 3 is an anion, the counter cation is not limited to sodium as long as it is a BF 4 salt, and H + , Li + ,
There is no problem even if it is K + , Rb +, or the like. Also NaBF 4
If the addition concentration of is within the range of 0.01 mol / l to 1 mol / l, it can be driven without problems, but in particular 0.05 m
It is preferably in the range of ol / l to 0.5 mol / l.
【００１２】また今回は３電極法による評価によって発
明の効果を確認したが、例えばプルシアンブルーや酸化
タングステン（ＷＯ3 ）あるいは金属フタロシアニンの
ように還元反応が安定なエレクトロクロミック材料を対
向極材料として使用すれば、容易に赤色表示可能なエレ
クトロクロミック表示部材の素子化が可能であることは
言うまでもない。Further, this time, the effect of the invention was confirmed by evaluation by the three-electrode method. For example, an electrochromic material having a stable reduction reaction such as Prussian blue, tungsten oxide (WO 3 ) or metal phthalocyanine was used as the counter electrode material. Needless to say, the electrochromic display member capable of displaying red color can be easily formed into an element.
【００１３】[0013]
【発明の効果】以上述べたように、電解析出法により得
られた鉄−フェナントロリン錯体を用いたエレクトロク
ロミック表示素子において、その駆動用電解液に四フッ
化ホウ素酸塩水溶液を使用した結果、繰り返し駆動寿命
が従来の水溶液系に比べて数倍改善される効果が得られ
た。このことによりエレクトロクロミック表示素子を構
成するためのシール剤として有機高分子系の接着剤が使
用できるようになり、従来困難であった赤色表示可能な
エレクトロクロミック表示素子の提供を実現できる。As described above, in the electrochromic display device using the iron-phenanthroline complex obtained by the electrolytic deposition method, as a result of using the tetrafluoroborate aqueous solution as the driving electrolyte solution, The effect that the repeated driving life was improved several times as compared with the conventional aqueous solution system was obtained. As a result, an organic polymer adhesive can be used as a sealant for constructing an electrochromic display element, and it is possible to provide an electrochromic display element capable of displaying red, which has been difficult in the past.
【図１】Ｆｅ（ＢＰＤＰ）3 の構造式である。FIG. 1 is the structural formula of Fe (BPDP) 3 .
【図２】エレクトロクロミック表示素子の断面図であ
る。FIG. 2 is a sectional view of an electrochromic display element.
【図３】繰り返し駆動寿命の評価結果である。FIG. 3 is a result of evaluation of repeated driving life.
１、８ 透明基板 ２、７ 透明導電膜 ３ シール材 ４ 表示極エレクトロクロミック材料 ５ 背景材 ６ 対向極エレクトロクロミック材料 ９ 電解液 1, 8 Transparent substrate 2, 7 Transparent conductive film 3 Sealing material 4 Display electrode electrochromic material 5 Background material 6 Counter electrode electrochromic material 9 Electrolyte
フロントページの続き (72)発明者 英 謙二 長野県上田市常田３−15−１ 信州大学繊 維学部機能高分子学科内 (72)発明者 白井 汪芳 長野県上田市常田３−15−１ 信州大学繊 維学部機能高分子学科内Front page continued (72) Inventor Kenji Ei 3-15-1 Tsuneta, Ueda City, Nagano Prefecture Department of Functional Polymers, Shinshu University (72) Inventor Shiho Yoshi Shirai 3-15-1 Tsuneda, Ueda City, Nagano Prefecture Shinshu Faculty of Fiber Science and Technology, Department of Functional Polymers
Claims (1)
ントロリン錯体を表示極エレクトロクロミック材料とし
て用い、その酸化還元反応を利用することにより赤と無
色の表示が可能なエレクトロクロミック表示素子におい
て、電解液に四フッ化ホウ素酸塩水溶液を使用したこと
を特徴とするエレクトロクロミック表示素子。1. An electrochromic display element capable of displaying red and colorless by using an iron-phenanthroline complex capable of forming a film by electrolytic deposition as a display electrode electrochromic material and utilizing its redox reaction. An electrochromic display device characterized in that an aqueous solution of tetrafluoroborate is used as an electrolytic solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5271251A JP2934933B2 (en) | 1993-10-04 | 1993-10-04 | Electrochromic display device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5271251A JP2934933B2 (en) | 1993-10-04 | 1993-10-04 | Electrochromic display device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07104321A true JPH07104321A (en) | 1995-04-21 |
| JP2934933B2 JP2934933B2 (en) | 1999-08-16 |
Family
ID=17497474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5271251A Expired - Lifetime JP2934933B2 (en) | 1993-10-04 | 1993-10-04 | Electrochromic display device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2934933B2 (en) |
-
1993
- 1993-10-04 JP JP5271251A patent/JP2934933B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2934933B2 (en) | 1999-08-16 |
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